Stabilization of protein-fiber-containing textiles



2,915,419 Patented Dec. 1, 1%59 STABILIZATION F PROTEIN-FIBER-CONTAIN-IN G TEXTILES Robert Jenkintown, Pa., assignor to Rohm & Haas Company,Philadelphia, Pa.,' a corporation of Delaware No Drawing. ApplicationNovember 21, 1956- Serial No. 623,532

- 24 Claims. (Cl. 117-141) This invention relates to the treatment ofprotein-containing textile materials and to the products thereof. Itrelates more particularly'to a process of treating, textile materialscomprisingscale-surfaced protein fibers, such as wool andwool-containing. fabric, whereby the textile materials are stabilizedagainst shrinking and felting.

An object. of this invention is to provide a process for shrink-proofingand felt-proofing textiles containing scalesurfaced protein. fibers,whether of natural or artificial origin, through the use ofi aqueousdispersions of resins.

it is an object to shrink-proof and felt-proof the textiles withoutadversely affecting such other properties of the textile as wearingqualities, and tensile strength.

While this invention is principally concerned With" improvements of, andmore particularly the reduction of shrinkage and/or completestabilization of textile materialso'fproteinaceous types, and while theinvention is described primarily in terms of wool-containingtextiles,the invention embraces the treatment ofother proteincontainihg textilematerials, such as those made of 01' containing silk, mohair, fur,Aralac and other synthetic fibers which are producedfromzcasein,soybeans, collagen, et cetera, and especially scale-surfaced proteinfibers of either natural or artificial origin. The terms textile andtextile materials are used herein to include yarns, threads, and pliedyarns as such or in Woven, knitted, or otherwise formed fabrics, sheets,cloths andthe like. Such textile materials may contain only one kind 'ofproteinaceous fiber or a mixture of such fibers with other natural orsynthetic fibers, such as of cotton, linen, rayon, nylon, or polymers ofacrylonitrile.

The process of treating the textile materials in accordance with theinvention comprises impregnating them with an aqueous dispersion of apol'yester-arninoplast condensation product described in detail belowand then heating the textiles at a temperature which is at least as highas 212 F., but which is lower than the charring point of the textile.During the treatment of the textiles in this Way, a chemical reaction isbelieved'to take place between the proteinaceous portion of the textileand the condensate in the dispersion and at the same time furthercondensation takes place between the molecules of the condensateassuring complete infusibility andinsolubility in the impregnant. Thecondensate appears to be chemically bound to the textile and not merelydeposited as a dry coating on the fibers. As a result, the resinouscondensate is not leached or removed from the textile during subsequentwet-washing or dry-cleaning operations.

In accordance with the present invention,.it has been found that markedreduction in the shrinking and felting properties ofwool-containingtextiles can be obtained by the application. thereto of an aqueousdispersion containing, dispersed therein at a concentration such as toapply from 0.7% to 8% onthefab ric weight of a polyesteraminoplastcondensation product which has excellent curing qualities, producesfilms of good adhesion and hard ness, and. yet is aselfedispersibleinaqueous systems The condensation product used for the present inventionmay be generally characterized as the coreaction product of at least twocomponents (A) and (B) as follows:

(A) A special. polyester having an average molecular weight of about 800to 1500 containing hydroxyl groups available for condensation with theaminoplast and free carboxyl groups available for neutralization bymeans of ammonia, an amine, or a quaternary ammonium compound, and p (B)An aminoplast soluble in such organic solvents as butanol, isopropanoland monoalkyl ethers of diethylene glycol in which the alkyl group ismethyl, ethyl, or the like.

COMPONENT A Component A is a special low molecular weight polyestercontaining hydroxyl groups adapted to enable its coreaction with theaminoplast (Component B) and some carbonyl groups for neutralization.The acid number of Component A should be' between about 90 and about100. This polyester is formed by first condensing a dibasic aliphaticacid having from 5 to 10 carbon atoms with a polyol or a mixture thereofcontaining at least 25 mole percent-of a polyol having three or morehydroxyl groups therein; For example, the polyol may contain up to molepercent by weight of a diol, such as ethylene glycol, diethyle'n'eglycol, propylene glycol, dipropylene glycol, and trime'thylene glycol,1,3-butane-diol, 1,4-butane-diol, and 1-,5-pentane-diol. Examples of thepolyols containing more thantwo hydroxyl groups that may be used includeglycerin'e;- s'orb'itol, p'ehtaerythritol, inositol,tetramethylolcyclohexanol, diand poly-pentaerythritol, and so forth, buttri-methylolethane is preferred. Preferably, the proportion'of diol isnot over 50 mole percent of the entire polyol component, and, of course,the diol may be completely absent.

' The aliphatic-dicarboxylic acid that is used may be adipic' acid,succinic acid, glutaric acid, sebacic acid or the like; Preferably itcontains from 5 to 8 carbon atoms, both may contain 4 to 18 carbonatoms.

The'polyol and dibasic aliphatic acid are mixed in the proportionof 1.2to 1.8 moles of polyol to each mole of acid; preferably 1.2 to 1.5 molesof polyol being used for each mole of acid. The mixture is heated to atemperature within the range ofabout 200 to 260 C. either in thepresence of an inert gas, such as carbon dioxide, nitrogen, ar'g'on,helium, when atmospheric or higher pressures are employed. If desired, areduced pressure may be present during the reaction to remove the waterformed on esterification and to favor a shift in the equilibrium towardthe esterification product. Pressures of 20 to 50 mni. orm'ore absolutepressure may be used. Optionally, an esterification catalyst may beused, such as 0.1 to 1% of sulfuric acid, toluene-sulfonic acid, zincchloride, or phosphorus pentoxide. Such catalyst, however, is notnecessary. The reaction is carried out until the acid numbet isreduced'to a value of 10 or less. acid number is reduced to a value ofless than 5.

The polyester obtained has terminal hydroxyl groups and also somehydroxyl groups at intervals along the polyester molecule.

Instead of using the free dibasic acid itself as one of the startingmaterials in this esterificationreaction, there may housed the loweralkyl diesters of the dibasic acids, such' asthe dimethyl or diethylesters. Reaction in this case involves an ester interchange andsometimes has the advantageof yielding a product having less color. Inthis procedure. the alcohol liberated is boiled off.

Optionally, the polyester may be modified with a fatty acid'having 8 to30 carbon atoms, such as lauric acid, stearic -acid, oleic acid,linoleic acid, linolenic acid, palmitic' 'acid, and ricinolcic acid. Themodification may Preferably, the

3 be effected by directly reacting the fatty acid with the polyol orwith the hydroxyl-containing polyester; alternatively, the same resultmay be effected by transesterification, in which case an ester of thefatty acid, such as an ester thereof with glycerol, is reacted with thepolyol or the hydroxyl-containing polyester in the presence of asuitable catalyst, such as an alkali metal alkoxide. There should beused from 1 to 3 moles of polyol or polyol mixture to each mole of thefatty acid (or the equivalent thereof in the case of an ester thereofwhen transesterification is employed); preferably there is used fromabout 1.2 to 1.5 moles of polyol to each mole of acid or equivalent ofester. When modification with a fatty acid is resorted to, it ispreferable to react the mono-basic fatty acid or its ester (in the caseof transesterification) with the polyol or a part of it before thepolyol is reacted with the dibasic acid. Thus, when a modified polyesteris desired, the fatty acid or ester thereof, such as a fat or oil, isfirst mixed with the polyol or polyol mixture and the esterification ortransesterification with the monobasic fatty acid is carried out underthe same conditions as stated hereinabove in respect to theesterification with a dibasic acid. Thus, the temperature may be from200 to 260 C.; the pressure from 20 mm. absolute up to atmospheric orhigher, an inert gas being used preferably at atmospheric or higherpressures. Optionally, an esterification or transesterification catalystmay be used as before. The reaction is continued until the acid numberreaches a value of or less. Preferably, it is continued until the acidnumber reaches a value of less than 1. It is desirable that themonobasic acid be completely bound up in the ester product, and to thisend the most desirable condition is attained when the acid numberapproaches or reaches a value of zero. The esterification productobtained from the polyol and monobasic acid is then mixed with thedibasic acid and any additional amount of polyol needed to bring theproportion of polyol used in the entire condensation reaction to aproportion of between 1.2 to 1.8 moles of polyol to one mole of thedibasic acid. This esterification reaction is continued at the sameconditions as stated hereinabove in describing the preparation of thesimple polyester unmodified with monobasic acid. As in the previouscase, the reaction is continued until the acid number of the product isreduced to a value of 10 or less and preferably to a value of less than5. The oil-modified polyester in this instance has some of its hydroxylgroups esterified with monoacyl radicals derived from the fatty acid. Ofcourse, a mixture of fatty acids may be employed instead of a single oneand similarly a mixture of dibasic acids may be employed instead of asingle one whether an oil-modified polyester or an unmodified polyesteris to be prepared up to this point.

The unmodified or oil-modified polyester thus prepared is then reactedwith o-phthalic acid or o-phthalic acid containing lower alkylsubstituents in the benzene ring, such as methyl, ethyl, propyl, orbutyl substituents or with the anhydrides thereof. The use of theanhydridw are preferred because of their solubility in the polyester atthis stage and the ease of reaction of one carboxylic group thereof,apparently without appreciable reaction of both such groups which wouldlead to cross-linking, water-insolubility, and gelation. Any otherpolycarboxylic acid, such-as isophthalic acid or terephthalic acid,. hasnot been found satisfactory in this phase of the prep-- aration of thepolyester, either because of insolubility and. lack of reactivitytherein, or, in some instances, because of rapid cross-linking to aWater-insoluble, gel stage- The amount of the phthalic acid or itsderivative or anhydride used is in the proportion of 2 to 3.5 moles forevery 3 moles of the polyol. When the polyol consists entirely of onecontaining 3 hydroxyl units, it is preferred to use approximately 2moles of the phthalic acid for 3 moles of the polyol. The reaction withthe phthalic acid is believed to provide terminal carboxyphenyl groupson the polyester molecules. The reaction of the mixture of phthalic acidwith theunmodified or oil-modified polyester may be effected at atemperature of 150 to 170 C. for a period of 1 to 2 hours. The reactionis continued until the acid number is reduced to 100 but is stoppedbefore the acid number is reduced appreciably below 90. When the desiredacid number within the range of 90 to 100 is reached, the reactionmixture is cooled to a temperature below C. and preferably down to 20 or30 C. to stop the esterification reaction. The reaction product therebyobtained provides Component A for reaction as will be describedhereinbelow.

COMPONENT B Component B consists of an alkylated polymethylol nitrogencompound obtained by the reaction of formaldehyde or substances yieldingformaldehyde and certain alcohols on a nitrogen compound selected fromthe group consisting of urea, thiourea, N,N'-ethyleneurea(imidazolidinone-Z), and triazines including guanamines, such asacetoguanamine and benzoguanamine, melamine and substituted melamines.The alkylation should be that resulting from an alcohol having from 3 to6 carbon atoms, such as isopropanol, n-propanol, butanol, pentanol,hexanol, or cyclohexanol, so that the aminoplast will be soluble in suchsolvents as butanol, isopropanol, pentanol and the like. Examples of thesubstituted melarnines include N,N-dialkylmelamines in which the alkylgroup has from 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl,isopropyl, and n-butyl, also N,N'-dialkylmelamines in which the alkylgroup may be any of those just stated, N-monoalkylmelamines in which thealkyl group may be any of those just stated. The preparation of thealkylated polymethylol nitrogen-containing compound is in itself no partof the present invention since these condensation products are wellknown and available commercially.

l. Condensation product obtained by coreaction of Components A and B Thecondensation product of Components A and B may be obtained by reacting amixture of them in organic solvents at a concentration of 50 to 90%solids; for example, Component A may be dissolved in xylene, benzene,toluene, ketones, such as dioxane or methylethyl ketone, or in monoalkylethers of ethylene glycol, such as the monobutyl ether, butanol ormixtures of such solvents. Similarly, the aminoplast (Component B) maybe dissolved in butanol or a mixture of butanol and xylene or in anyother mixture of the various solvents just mentioned. Component A andComponent B are reacted in proportions of about 40 to 60 parts by weightof Component A to about 60 to 40 parts by weight of Component B.Preferably, the concentration of the reactants in the organic solvent,and consequently of the reaction product therein, is maintained as highas possible consistent with manipulability which depends upon I theviscosity. The reaction of the mixture is effected in the organicsolvent solution at a temperature of 50 to 120 C., and preferably at atemperature of 70 to C., at atmospheric pressure. The reaction iscarried out until a sample to which an amine (such as 10% oftriethylamine on weight of condensate solids) is added is soluble inwater. Generally, the reaction is accompanied by an advance in viscosityof about 3 to 10 poises when measured at 60% solids concentration in anyparticular organic solvent at room temperature.

The reaction product is cooled below 60 C., such as to 25 to 55 C., andthen it is neutralized or at least partially neutralized with ammonia,an amine, or a quaternary ammonium compound. If desired, a smallproportion of the neutralizing component may be a fixed base, such aspotassium or sodium hydroxide, or carbonates. Ho ever, it is preferredtouse as the entire neuof such -materials.

i tra-lizing agent eitherzammofrimua volatile vamine or a quaternaryammonium compound or a mixture of '2 or 3 When ammonia .is theneutralizing agent, it is generally introduced=,as zan aqueous solution.Preferably the ammonia is'rather concentrated when it is desired tostore or ship the productin order to save bulk. However, the ammonia may'be sufficiently dilute to directly produce an aqueous solution ordispersion of .the condensation product of :the present invention havingthe desired solids conceutrationfor :direct application to the textile.When an amine or a quaternary ammonium compound is used as theneutralizing agent, it may be added without adding Water so thatLtheneutralized condensation product of the invention isessentiallyanhydrous but is capable of practically unlimited dilution with waterwithout being coagulated. Such amines as monoethylamine, triethylamine,dimethylamine, trimethylamine, and morpholine are quite suitable asneutralizing agents. Also quaternary ammonium compounds, such ascholine, trimethylbenzylammonium chloride,octadecylbenzyldimethylammonium chloride, methylpyridinium chloride, maybe used for neutralization. As inthe case of the amines, they may beused Without the addition of water so that the product is obtained as asubstantially anhydrous solution which is dilutable withwater topractically unlimited extent. If desired, the amines or the quaternaryammonium compounds may be introduced as aqueous solutions and, in thecase of ammonia, a dilution may be such as to provide the concentrationof the condensation product desired for application. On the other hand,the substantially anhydrous products obtained by neutralization by anamine or a quaternary ammonium compound may be stored or shipped in thatconcentrated form and then diluted with Water for application atzthe'point of its destined use.

COMPONENT C Component C, when used, may be any of the common alkydresins including oil-modified alkyd resins. For example, simple alkydsthat may be used may be those obtained by condensing a dicarboxylic.acid, such as ophthalic, terephthalic, isophthalic, pyromellitic,succinic, glutaric, adipic or sebacic acids, with a polyhydric alcohol,such as ethylene glycol, diethylene glycol, glycerol,

. pentaerythritol, sorbitol, inositol, trimethylolethane,tetramethylolcyclohexanol, diand poly-pentaerythritol. Preferably thepolyhydric alcohol component from which the alkyd is derived comprisesat least 25% by weight of at least one alcohol containing at least threehydroxyl groups in order to provide an excess of hydroxyl groupsavailable for reaction with the aminoplast (Component B). If desired,there may be used as a part of the dicarboxylic acid component one ormore ethylenically unsaturated acids, such as maleic acid, fumaric acid,or the polycarboxylic acid compounds obtained by interacting maleicanhydride with abietic acid, ricinoleic or eleostearic acids. Theunsaturated dicarboxylic acid may amount to fifty percent of the totaldicarboxylic acid used, but is preferably not over 25% of such total.

The alkyds may be modified with a higher monobasic aliphatic acid having12 to 30 carbon atoms, such as a fatty acid or fatty acid mixturederived from drying, semidrying, or non-drying oils or fats in which thefatty acid has from 12 to 30 carbon atoms and up. The modifying fattyacid may be lauric acid, myristic acid, coconut oil fatty acids, palmoil fatty acids, palmitic acid, oleic acid, stearic acid, linolenicacid, or fatty acids obtained by hydrogenation of fish, animal, orvegetable oils or fats.

In preparing the alkyd, the glycerol or other polyhydric alcohol ormixture thereof may first be partially esterified with the monoacid ormixture thereof, and the resulting partial ester may then be reactedwith the dicarboxylic acid, such as phthalic acid. Alternatively, thedicar- 'boxylic acid, the polyhydric alcohol and the monocar- .boxylicacid may be mixed together and reacted simultaneously. Jim's preferredto usealkyds'modified'with essentially saturated,-non-drying fatty acidsto assure'freedom from yellowing and embrittlement on ageing. Preferredalkyds may be obtained from 39 to 50% phthalic acid, 20 to. 30%glycerol, and 30 to 35% coconut fatty acids. The preparation of thealkyd is in itself no part of the present invention, since conventionaloilmodified alkyds may be used.

The alkyd of which Component C is constituted is essentially awater-insoluble product that is soluble in organic solvents, such asbutanol, pentanol, .the monoethyl ether of ethylene glycol and the likeand has an average molecular weight of about 2000 to about 10,000.

Such alkyds have excellent film-forming qualities but are not adapted tobe appliedfrom aqueous systems in the production of coatings or othermaterials.

ll. Condensation product obtained .by coreaction of Components A, B, andC The condensation product of Components A, B, and C is obtained byfirst reacting the aminoplast (Component B) with the alkyd (ComponentC). They may be reacted in organic solvents at a concentration of 50 tosolids; for example, Component C may be dissolved in xylene, benzene,toluene, ketones, such as dioxane or methylethyl ketone, or in monobutylether of ethylene glycol, butanol or mixtures of such solvents.Similarly, the aminoplast (Component B) may be dissolved in butanol or amixture of butanol and xylene or in any other mixture of the varioussolvents just mentioned. Component B and Component C are reacted inproportions of about 20 to 30 parts by weight of Component C to about 20to 30 parts by weightof Component B. The reaction of the mixture iseffected in the organic solvent solution at a temperatore of 60 to 120C., and preferably at a temperature of 70 to C., at atmosphericpressure. The reaction is carried out until an advance in viscosity ofat least 3 poises is obtained when measured at 60% solids concentrationin any particular organic solvent at room temperature.

The organic solvent solution of the reaction product of B and C is thenmixed With the polyester Component A whether unmodified or oil-modifiedin proportions of about 40 to 60 parts by Weight of Component A,preferably about 50 parts thereof, to 50 parts by weight of the reactionproduct of B and C. Component A may be added to the reaction product ofB and C as such or it may be dissolved first in an organic solvent, suchas toluene, xylene, benzene, or monoalkyl ethers of ethylene glycol,such as the monobutyl ether thereof, at concentrations of 50 to 90%solids, preferably as high as possible consistent with the working ofviscous medium. The reaction is effected in the organic solvent solutionat 50 to 80% solids content at a temperature of about 60 C. for aboutone-half hour. Preferably, the concentration of the reactants in theorganic solvent, and consequently of the reaction product therein, ismaintained as high as possible consistent with manipulability whichdepends upon the viscosity. This reaction is continued for a timesuflicient to raise the viscosity at least 2 poises when measured at 60%solids concentration in an organic solvent at room temperature.

The reaction product is cooled below 60 (3., such as to 25 to 55 C., andthen it is neutralized or at least partially neutralized with ammonia,an amine, or a quaternary ammonium compound. If desired, a smallproportion of the neutralizing component may be a fixed base, such aspotassium or sodium hydroxide, or carbonates. However, it is preferredto use as the entire neutralizing agent either ammonia, a volatile amineor a quaternary ammonium compound or a mixture of two or three of suchmaterials. When ammonia is the neutralizing agent, it is generallyintroduced as an aqueous solution. Preferably the ammonia is ratherconcentrated when it is desired to store or ship the product in order tosave bulk. However, the ammonia may be sufficiently dilute to directlyproduce an aqueous solution or dispersion of the condensation product ofthe present invention having the desired solids concentration for directapplication. When an amine or a quaternary ammonium is used as theneutralizing agent, it may be added without adding water so that theneutralized condensation product of the invention is essentiallyanhydrous but is capable of practically unlimited dilution with waterwithout being coagulated. Such amines as monoethylamine, triethylamine,dimethylamine, trimethylamine, and morpholine are quite suitable asneutralizing agents. Also, quaternary ammonium compounds, such ascholine, trimethylbenzylammonium chloride, octadecylbenzyldimethylammonium chloride, and methylpyridinium chloride, maybe used for neutralization. As in the case of the amines, they may beused without the addition of water so that the product is obtained as asubstantially anhydrous solution which is dilutable with water topractically unlimited extent. If desired, the amines or the quaternaryammonium compounds may be introduced as aqueous solutions and, in thecase of ammonia, a dilution may be such as to provide concentration ofthe condensation product desired for application. On the other hand, thesubstantially anhydrous products obtained by neutralization by an amineor a quaternary ammonium compound may be stored or shipped in thatconcentrated form and then diluted with water for application at thepoint of its destined use.

The proportion of the condensate that is applied to the fabric may varyfrom 0.7 to 8% by weight of the fabric, a proportion of 2.5 to beingpreferred. The concentration of the aqueous dispersion may be variedaccordingly depending on pick-up. When about 50 to 60% pick-up isemployed, the concentration will be from 1.5 to 15% and preferably fromabout 5 to 10%. The dispersion is deposited on the textile material bysuch means as exhausting, spraying, or dipping. What is required is thatthe textile material be saturated and im pregnated by the dispersion.This can be done at any desired temperature short of the boiling pointof the dispersion. Ordinarily the textile is padded at room temperaturewith the dispersion.

The impregnated textile material must then be heated at a temperaturebetween 212 F. and 400 F. for a period of about one-half minute to 30minutes, the higher the temperatures, the shorter the period required. Aflash cure at temperatures above 400 F., even up to 700 F. for shortperiods of five to ten seconds, may be employed. In any event, the timeand temperature should not be such as to damage the fabric. Preferablythis heating is eifected at a temperature from 240 F. (for about 10 tominutes) to about 310 F. (for about 5 to 10 minutes), and it is believedthat it efiects some chemical reaction involving the condensate andpossibly the textile. In any event, the heating sets the condensate onthe textile, and especially in the case of wool, reduces shrinkage and/or imparts full dimensional stability thereto. Drying of the treatedtextile and the heat-treatment which effects the chemical reaction canbe carried out simultaneously or concurrently in one step, or thetextile can be substantially or completely dried at a conveniently lowertemperature and then heated later at the higher temperature. As will beevident to those skilled in the art, the optimal length of the heatingperiod depends on the particular temperature which is employed, on theparticular condensate, and on the quantity thereof which is on thetextile. But in any case the heat-treatment does not require a longperiod and is usually measured in minutes, generally one to thirtyminutes and preferably about five to fifteen minutes. The mostsatisfactory time of heating for any particular combination ofdispersion and textile is readily determined by heating pieces of theimpregnated textile for varying lengths of time at a given temperatureand then measuring the resultant stabilization of the individual piecesby means of a wetwashing test.

The treated textiles are characterized by greater resistance to abrasionand/or reduced shrinkage and, in many cases, fully practical dimensionalstability against laundering, by which is meant that they aresubstantially shrink-proof. They do not stiffen, degrade or discolor onageing or on exposure to ultraviolet light.

The effectiveness of the dispersions exemplified below in stabilizingwool was determined by impregnating measured pieces of flannel withthem, drying, and heating the impregnated pieces of flannel at atemperature of 240 F. or higher, laundering the pieces in hot water,then drying them and measuring the shrinkage. In these tests pieces ofwoolen flannel (2/2 right hand 45 twill, 55 x 44; S-twist in ends, Z inpicks; scoured, carbonized, neutralized and bleached) were used. Allpieces were 10 inches square, with axes along the yarn systems. Thepieces of flannel were padded with a pad liquor of the resin dispersionwhich was so adjusted in solids-content as to provide the desired amountof resin solids. The treated specimens were dried and heated and curedat a temperature of at least 240 F. The specimens were washed, togetherwith untreated pieces of flannel, in a Cascade wheel washer containing70 grams of soap (Ivory) in 10 gallons of water for five hours. In allcases the load in the washer was made up to three pounds with woolfabrics and the temperature was maintained at F. The values of shrinkageare given as percentage reduction in the initial area after taking intoaccount any inherent residual shrinkage in the initial fabric that maybe present as a result of previous drying under tension and is removableby simply wetting and drying. In other words, the shrinkage valueshereinbelow are obtained by subtracting relaxation shrinkage from theactual shrinkage measured.

The following examples serve to illustrate the invention and parts andpercentages are by weight unless otherwise indicated:

PREPARATION OF CONDENSATES 1. Component A EXAMPLE A Into a reactionvessel, there are introduced 292 grams of adipic acid (2.0 moles) and360 grams of trimethylolethane (3 moles). Heat and reduced pressure areapplied and the batch held at 230 C. until the acid number value fallsbelow 4.0. The reaction mixture is then cooled to ca. 160 C., vented and296.0 grams of o-phthalic anhydride (2.0 moles) is charged. The mixtureis heated to to C. at atmospheric pressure and held at this temperatureuntil the acid number of the batch falls to ca. 100. At this point, fullcooling is applied to the batch and suflicient xylol is charged toadjust the solids content of the batch to ca. 85%.

EXAMPLE B The procedure of Example A is repeated replacing the adipicacid with 404.0 grams of sebacic acid (2 moles) and the polyol with332.0 grams of glycerine (3.6 moles).

EXAMPLE C The procedure of Example A is repeated replacing the adipicacid with 236.0 grams of succinic acid (2 moles) and the polyol with437.0 grams of sorbitol (2.4 moles).

EXAMPLE D 112,2 moles) and 96.0 grams of trimethylolethane (0.8 mole).

EXAMPLE F 200 grams (1.0 mole) of lauric acid and 156.0 grams (1.3moles) of trimethylolethane are heated under reduced pressure (totalpressure=ca. 30 mm. Hg) to a temperature of 230 C. The mixture is heldat this temperature until the acid number of the batch (mg. KOH reqd. toneutralize 1.0 gram) falls below 1.0. The system is then cooled to below170 C., vented and 292.0 grams of adipic acid (2.0 moles) and 204.0grams of trimethylolethane (1.7 moles) are charged. Heat and reducedpressure are re-applied and the batch again held at 230 C. until theacid number value falls below 4.0.

The reaction mixture is then cooled to ca. 160 C., vented and 296.0grams of o-phthalic anhydride (2.0 moles) is charged. The mixture isheated to 150 C. to 160 C. at atmospheric pressure and held at thistemperature until the acid number of the batch falls to ca. 100. At thispoint, full cooling is applied to the batch and sufiicient -xylol ischarged to adjust the solids content of the batch to ca. 85%.

EXAMPLE G The procedure of Example F is followed substituting 364.0grams of sebacic acid (1.8 moles) for the adipic acid.

EXAMPLE H The procedure of Example F is followed substituting 138.0grams of diethylene glycol (1.3 moles) for the first charge oftrimethylolethane.

EXAMPLE I The procedure of Example F is followed substituting 264.0grams of glutaric acid (2 moles) for the adipic acid and 120.0 grams ofglycerol (1.3 moles) for the first charge of trirnethylolethane.

EXAMPLE .T

The procedure of Example F is followed substituting 427.0 grams ofstearic acid (1.5 moles) for the lauric acid.

EXAMPLE K Charge 444 grams of soybean oil to a reaction vessel alongwith 120 grams of trimethylolethane (1.0 mole). Heat is applied to themixture and nitrogen gas is sparged through the batch continuouslythroughout the reaction. At 130 C., 1.0 gram of a 25 solution of sodiummethylate in methanol is added to the batch. The heating is continued.At 165 C., 0.5 gram of triphenylphosphite is charged to the batch.Heating is continued to a batch temperature of 230 to 240 C. The mixtureis held in this temperature range about five minutes until a clear pillis obtained in cooled droplets from a rod dipped into the mixture. Themixture is then cooled to approximately 180 C., at which point there ischarged 438 grams (3 moles) of adipic acid and also another 360 grams (3moles) of the trimethylolethane, and heating is once more resumed. Thebatch is heated to 260 and held at this temperature until the acidnumber drops to less than 2.0. Then the batch is cooled to 170 C. and444 grams (3 moles) of phthalic anhydride are charged. Heating is againresumed. The batch is heated to 150 to 160 C. until the acid numberdrops to 90 to 100 C., at which point the reaction is probably completeand full cooling is applied. At a temperature of 110 C., the batch isdiluted to about 85% solids with 300 grams of xylol.

EXAMPLE L The procedure of Example K is repeated substituting 444.0grams of coconut oil for the soybean oil.

ll. Condensales formed of Components A and B EXAMPLE M A mixture-of 100grams of a 60% solution in xylene of-a butylated polymethylolmelamineand 100 grams of the polyester product .of Example A is stirred at room.temperaturefor-about one-half hour to insure reasonably thorough mixingbefore any heat is applied. The mixture is then heated to 55 to 60C. andheld in this range for one-half hour. At the end of this time, reactionis stopped by applying cooling to the batch and adding an amount ofconcentrated 28% aqueous NH or triethylamine (100%) equal to 20% of theweight of polyester solids present.

EXAMPLE N The procedure of Example M is followed substituting 120 gramsof the polyester of Example F for the polyester of Example A therein.

EXAMPLE 0 The procedure of Example N is repeated in successive runssubstituting for the polyester there used 120 grams of each of thepolyesters of Examples B to E and G to L.

EXAMPLE P The procedure of Example N is followed except that 120 gramsof the polyester of Example K is substituted for the polyester ofExample F.

EXAMPLE Q The procedure of Example M is repeated except that.

100 grams of a 50% solution of a butylated dimethylol-- urea issubstituted for the melamine resin.

EXAMPLE R The procedure of Example M is repeated except that 100 gramsof a 45% solution of N,N-diisopropoxymethyl-imidazolidinone-Z issubstituted for the melamine resin.

EXAMPLE S The procedure of Example N is repeated substituting 100 gramsof a 60% solution in xylene of a butylatedpolymethylol-N,N-dimethylmelamine.

III. C ondensates formed of Components A, B, and C EXALIPLE T A mixtureof 100 grams of a 60% solution in xylene of a butylatedpolymethylolmelamine and 100 grams of a 60% solution in xylene of acoconut oil-modified glycerol-phthalic acid alkyd resin is heated withagitation to 70 to C. at atmospheric pressure. The mixture is held atthis temperature with continuous agitation until the viscosity of thebatch advanced about 15 poises from its original viscosity (whenmeasured at 25 C. and at a 60% concentration). The reaction is thenstopped by cooling the batch to room temperature. During the cooling,there is gradually added grams of the polyester product of Example A.

The entire mixture is stirred at room temperature for ca. /2 hour toinsure reasonably thorough mixing before any heat is applied. Themixture is then heated to 55 to 60 C. and held in this range forone-half hour. At the end of this time, reaction is stopped by applyingcooling to the batch and adding an amount of concentrated aqueous NH(ca. 28%) or triethylamine (100%) equal to 20% of the weight ofpolyester solids present.

EXAMPLE U The procedure of Example-T is followed substituting grams ofthe polyester of Example F for the polyester of Example A therein used.

The coreaction product obtained is neutralized with tri- .ethylamine.

EXAMPLE V The procedure of Example U is repeated in successive runssubstituting for the polyester there used 120 grams 'of each of thepolyesters of Examples B to E and G to L.

EXAMPLE W The procedure of Example U is followed except that 120 gramsof the polyester of Example K is substituted for the polyester ofExample F and 100 grams of a 60% solution in xylene of a linseedoil-modified glycerol phthalate is substituted for the alkyd solutionthere used.

EXAMPLE X The procedure of Example T is repeated except that 100 gramsof a 50% solution of a butylated dimethylolurea is substituted for themelamine resin.

EXAMPLE Y The procedure of Example T is repeated except that 100 gramsof a 45% solution of N,N-diisopropoxymethyl-imidazolidinone-Z issubstituted for the melamine resin.

EXAMPLE Z The procedure of Example U is repeated substituting 100 gramsof a 60% solution in xylene of a butylatedpolymethylol-N,N-dimethylmelamine.

IV. Stabilization of fabrics EXABIPLE 1 (a) A wool flannel as describedabove is impregnated with an aqueous dispersion obtained from theammonianeutralized product of Example P diluted with water to a solidsconcentration at a wet pick-up of about 50% on the weight of the fibers.Heating for minutes at 250 F. dries and cures the condensate on thefabric. The fabric carries 2.5% of the condensate and after thefive-hour wash shows a shrinkage of 2%. The untreated control fabricshows 42% shrinkage.

(b) The same procedure using a concentration of 10% applies 5%condensate and the fabric obtained has zero shrinkage.

EXAMPLE 2 (a) A wool flannel as described above is impregnated with anaqueous dlispersion obtained from the ammonianeutralized product ofExample T diluted to 5% solids concentration. Heating for 10 minutes at250 F. dries and cures the condensate on the fabric. The fabric carries2.5 of the condensate and after the five-hour wash shows a shrinkage of16%. The untreated control fabric shows 45% shrinkage.

(b) The same procedure using a concentration of 10% applies 5%condensate and the fabric obtained has 4% shrinkage.

EXAMPLE 3 (a) By separately repeating the procedure of Example 1(a) witheach of the condensates of Examples M, N, O, Q, R, and S with a knittedwoolen fabric, which untreated shows a shrinkage of 63%, shrinkages inthe treated fabrics are obtained which range from 3 to 12%.

(b) By separately repeating the procedure of Example 1(b) with each ofthe condensates of Examples M, N, O, Q, R, and S with a knitted woolenfabric, which untreated shows a shrinkage of 63%, shrinkages in thetreated fabrics are obtained which range from zero to 4%.

EXAMPLE 4 (a) The procedure of Example 2(a) is repeated separately witha fabric as defined in Example 2(a) using the condensates of Examples U,V, W, X, Y, and Z. The untreated fabric shows a shrinkage of 53%. Thetreated fabrics show shrinkages in the range of 5% to (b) By repeatingthe procedure of part (a) hereof with dispersions containing 10% of therespective condensates, the treated fabrics show shrinkages in the rangefrom 1 to 5%.

It is to be understood that changes and variations may be made withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

I claim:

I. As an article of manufacture, a textile material containing proteinfibers modified by 0.7 to 8% by weight of an insoluble product obtainedby the heating of an impregnan-t thereon comprising a salt of a memberselected from the group consisting of ammonium hydroxide, volatileamines, and quaternary ammonium hydroxides with a condensation productof 40 to 60 parts by weight of an organic solvent-soluble (C -Calkylated condensate of formaldehyde with a compound selected from thegroup consisting of urea, thiourea, imidazolidinone-2, acetoguanamine,benzoguanamine, melamine, and monoand di-(C -C )alkylme1amines with 40to 60 parts by weight of a polyester having an average molecular weightof about 800 to 1500 containing hydroxyl groups, free carboxyl groups,and an acid number between about 90 and about 100, the polyester being acondensation prodnet of an aromatic member selected from the groupconsisting of o-phthalic acid, o-phthalic acid containing lower alkylsubstituents in the ring and their anhydrides with a condensationproduct selected from the group consisting of (a) polyesters having anacid value of not over 10 and obtained from the condensation of amixture of at least one dibasic aliphatic acid having 5 to 10 carbonatoms with a polyol material containing at least 25 mole percent of atleast one polyol containing at least three hydroxyl groups, theproportions in the mixture being in the range of 1.2 to 1.8 moles ofpolyol to each mole of acid, and (b) polyesters as obtained in (a) butmodified by condensation with a fatty acid having 8 to 30 carbon atoms;the proportion of the aromatic member to the total polyol materialsbeing in the range of 2 to 3.5 moles of the former for each 3 moles ofthe latter.

2. An article of manufacture as defined in claim 1 in which said polyolconsists entirely of one or more polyols having at least three hydroxylgroups.

3. An article of manufacture as defined in claim 1 in which said polyolis trimethylolethane.

4. An article of manufacture as defined in claim 1 in which said polyolis pentaerythritol.

5. An article of manufacture as defined in claim 1 in which said polyolis glycerol.

6. An article of manufacture as defined in claim 1 in which said polyolis trimethylolethane and the dibasic aliphatic acid is adipic acid.

7. An article of maufacture as defined in claim 1 in which said polyolis trimethylolethane and the dibasic aliphatic acid is sebacic acid.

8. An article of manufacture as defined in claim 1 in which said polyolis trimethylolethane and the dibasic aliphatic acid is adipic acid andthe polyester is modified by lauric acid.

9. An article of manufacture as defined in claim 1 in which said polyolis trimethyoletha-ne and the dibasic aliphatic acid is adipic acid andthe polyester is modified by the acid of soybean oil.

10. An article as defined in claim 1 in which the textile materialcontains wool fibers.

11. As an article of manufacture, a textile material containing proteinfibers modified by 0.7 to 8% by weight of an insoluble product obtainedby the heating of an impregnant thereon comprising a salt of a memberselected from the group consisting of ammonium hydroxide, volatileamines, and quaternary ammonium hydroxides with the condensation productof 50 parts by weight of the reaction product of an alkyd and an organicsolventsoluble (C -C )alkylated condensate of formaldehyde with acompound selected from the group consisting of urea, thiourea,imidazolidinone-2, acetoguanarnine, benzoguanamine, melamine, andmonoand di-(C C )a1kylmelamines with 40 to 60 parts by weight of apolyester having an average molecular weight of about 800 to 1500containing hydroxyl groups, free carboxyl groups, and an acid numberbetween about 90 and about 100.

12. As an article of manufacture, a textile material containing proteinfibers modified by 0.7 to 8% by weight of an insoluble product obtainedby the heating of an impregnant thereon comprising a salt of a memberselected from the group consisting of ammonium hydroxide, volatileamines, and quaternary ammonium hydroxides with a condensation productof (A) a polyester containing hydroxyl groups, free carboxyl groups, andan acid number between about 90 and about 100, the polyester being acondensation product of an aromatic member selected from the groupconsisting of o-phthalic acid, o-phthalic acid containing lower alkylsubstituents in the ring and their anhydrides with a condensationproduct selected from the group consisting of (a) polyesters having anacid value of not over 10 and obtained from the condensation of amixture of at least one dibasic aliphatic acid having to carbon atomswith a polyol material containing at least 25 mole percent of at leastone polyol containing at least three hydroxyl groups, the proportions inthe mixture being in the range of 1.2 to 1.8 moles of polyol to eachmole of acid, and (b) polyesters as obtained in (a) but modified bycondensation with a fatty acid having 8 to 30 carbon atoms; theproportion of the aromatic member to the total polyol material being inthe range of 2 to 3.5 moles of the former for each 3 moles of thelatter, (B) an organic solventsoluble (C -C )alkylated condensate offormaldehyde with a compound selected from the group consisting of urea,thiourea, imidazolidinone-Z, acetoguanarnine, benzoguanamine, melamine,and monoand di-(C C alkylmelamines, and (C) an alkyd.

13. An article of manufacture as defined in claim 12 in which thecondensation product is formed of 40 to 60 parts of Component A for each50 parts of the condensation product of Components B and C and thelatter condensation product is formed of about 20 to 30 parts of B to 20to 30 parts of C.

14. As an article of manufacture, a textile materia containing proteinfibers modified by 0.7 to 8% by weight of an insoluble product obtainedby the heating of an impregnant thereon comprising a salt of a memberselected from the group consisting of ammonium hydroxide, volatileamines, and quaternary ammonium hydroxides with a condensation productof 50 parts by weight of the reaction product of an alkyd and an organicsolventsoluble (C C )alkylated condensate of formaldehyde with acompound selected from the group consisting of urea, thiourea,imidazolidinone-Z, acetoguanamine, benzoguanamine, melamine, and monoanddi-(C -CQalkyI- melamines with 40 to 60 parts by Weight of a polyesterhaving an average molecular weight of about 800 to 1500 containinghydroxyl groups, free carboxyl groups, and an acid number between about90 and about 100, the polyester being a condensation product of anaromatic member selected from the group consisting of o-phthalic acid,o-phthalic acid containing lower alkyl substituents in the ring andtheir anhydrides with a condensation product selected from the groupconsisting of (a) polyesters having an acid value of not over 10 andobtained from the condensation of a mixture of at least one dibasicaliphatic acid having 5 to 10 carbon atoms with a polyol materialcontaining at least 25 mole percent of at least one polyol containing atleast three hydroxyl groups, the proportions in the mixture being in therange of 1.2 to 1.8 moles of polyol to each mole of acid, and (b)polyesters as obtained in (a) but modified by condensation with a fattyacid having 8 to 30 carbon atoms; the proportion of the aromatic memberto the total polyol material being in the range of 2 to 3.5 moles of theformer for each 3 moles of the latter.

15. An article of manufacture as defined in claim 14 in which the saltis a quaternary ammonium salt.

16. An article of manufacture as defined in claim 14 in which the saltis an ammonium salt.

17. An article of manufacture as defined in claim 14 in which the saltis an amine salt.

18. An article of manufacture as defined in claim 14 in which the saltis a triethylamine salt.

19. An article of manufacture as defined in claim 18 in which the polyolis trimethylolethane and the dibasic aliphatic acid is adipic acid andthe polyester is modified by lauric acid.

20. An article of manufactureas defined in claim 19 in which theaminoplast is a butylated polymethylolmelamine and the alkyd is acoconut oil-modified glycerol phthalate.

21. An article of manufacture as defined in claim 18 in which the polyolis trimethylolethane, the dibasic acid is adipic acid, the polyester ismodified by soybean oil acids, the alkyd is a linseed oil-modifiedglycerol phthalate, and he aminoplast is a butylatedpolymethylol-melamine.

22. A process for treating proteinaceous textile materials to reduce theshrinkage thereof comprising impregnating such a material with anaqueous dispersion containing about 1.5 to 15% by weight of a salt of amember selected from the group consisting of ammonium hydroxide,volatile amines, and quaternary ammonium hydroxides with a condensationproduct of 40 to 60 parts by weight of an organic solvent-soluble (C C)alkylated condensate of formaldehyde with a compound selected from thegroup consisting of urea, thiourea, imidazolidinone-Z, acetoguanamine,benzoguanamine, melamine, and monoand di-(C -C )alkylmelamines with 40to 60 parts by weight of a polyester having an average molecular weightof about 800 to 1500 containing hydroxyl groups, free carboxyl groups,and an acid numberbetween about and about 100, the polyester being acondensation product of an aromatic member selected from the groupconsisting of o-phtnalic acid, o-phthalic acid containing lower alkylsubstituents in the ring and their anhydrides with a condensationproduct selected from the group consisting of (a) polyesters having anacid value of not over 10 and obtained from the condensation of amixture of at least one dibasic aliphatic acid having 5 to 10 carbonatoms with a polyol material containing at least 25 mole percent of atleast one polyol containing at least three hydroxyl groups, theproportions in the mixture being in the range of 1.2 to 1.8 moles ofpolyol to each mole of acid, and (b) polyesters as obtained in (a) butmodified by condensation with a fatty acid having 8 to 30 carbon atoms;the proportion of the aromatic member to the total polyol material beingin the range of 2 to 3.5 moles of the former for each 3 moles of thelatter, drying and heating the treated textile at a temperature of 212to 700 F. for a period of about 5 seconds to about 30 minutes butinsufficient to damage the fabric.

23. A process as defined in claim 22 in which the textile materialcontains wool fibers.

24. A process for treating proteinaceous textile materials to reduce theshrinkage thereof comprising impregnating such a material with anaqueous dispersion containing about 1.5 to 15% by weight of a salt of amember selected from the group consisting of ammonium hydroxide,volatile amines, and quaternary ammonium hydroxides with thecondensation product of 50 parts by weight of the reaction product of analkyd and an organic solvent-soluble (C C )alkylated condensate offormaldehyde with a compound selected from the group consisting of urea,thiourea, imidazolidinone-2, acetoguanamine, benzoguanamine, melamine,and monoand di-(C C )alkylmelamines with 40 to 60 parts by weight of apolyester having an average molecular weight of about 800 to 1500containing hydroxyl groups, free carboxyl groups, and an acid numberbetween about 90 and about 100, drying and heating the treated textileat a temperature of 212 to 700 F. for a period of about 5 seconds toabout 30 minutes but insuflicient to damage the fabric.

References Cited in the file of this patent UNITED STATES PATENTS.

2,471,396 Light May 29, 1949 2,518,267 Baird et a1. Aug. 8, 19502,720,500 Cody Oct. 11, 1955 2,763,649 Albrecht Sept. 18, 1956

1. AS AN ARTICLE OF MANUFACTURE, A TEXTILE MATERIAL CONTAINING PROTEINFIBERS MODIFIED BY 0.7 TO 8% BY WEIGHT OF AN INSOLUBLE PRODUCT OBTAINEDBY THE HEATING OF AN IMPREGNANT THEREON COMPRISING A SALT OF A MEMBERSELECTED FROM THE GROUP CONSISTING OF AMMONIUM HYDROXIDE, VOLATILEAMINES, AND QUATERNARY AMMONIUM HYDROXIDES WITH A CONDENSATION PRODUCTOF 40 TO 60 PARTS BY WEIGHT OF AN ORGANIC SOLVENT-SOLUBLE (C3-C5)ALKYLATED CONDENSTATE OF FORMALDEHYDE WITH A COMPOUND SELECTED FROM THEGROUP CONSISTING OF UREA, THIOUREA, IMIDAZOLIDINONE-2, ACETOGUANAMINE,BENZOGUANAMINE, MELAMINE, AND MONOAND DI-(C1-C4) ALKYLMELAMINES WITH 40TO 60 PARTS BY WEIGHT OF A POLYESTER HAVING AN AVERAGE MOLECULAR WEIGHTOF ABOUT 800 TO 1500 CONTAINING HYDROXYL GROUPS, FREE CARBOXYL GROUPS,AND AN ACID NUMBER BETWEEN ABOUT 90 AND ABOUT 100, THE POLYESTER BEING ACONDENSATION PRODUCT OF AN AROMATIC MEMBER SELECTED FROM THE GROUPCONSISTING OF O-PHTHALIC ACID, O-PHTHALIC ACID CONTAINING LOWER ALKYLSUBSTITUENTS IN THE RING AND THEIR ANHYDRIDES WITH A CONDENSATIONPRODUCT SELECTED FROM THE GROUP CONSISTING OF (A) POLYESTERS HAVING ANACID VALUE OF NOT OVER 10 AND OBTAINED FROM THE CONDENSATION OF AMIXTURE OF AT LEAST ONE DIBASIC ALIPHATIC ACID HAVING 5 TO 10 CARBONATOMS WITH A POLYOL MATERIAL CONTAINING AT LEAST 25 MOLE PERCENT OF ATLEAST ONE POLYOL CONTAINING AT LEAST THREE HYDROXYL GROUPS, THEPROPORTIONS IN THE MIXTURE BEING IN THE RANGE OF 1.2 TO 1.8 MOLES OFPOLYOL TO EACH MOLE OF ACID, AND (B) POLYESTERS AS OBTAINED IN (A) BUTMODIFIED BY CONDENSATION WITH A FATTY ACID HAVING 8 TO 30 CARBON ATOMS;THE PROPORTION OF THE AROMATIC MEMBER TO THE TOTAL POLYOL MATERIALSBEING IN THE RANGE OF 2 TO 3.5 MOLES OF THE FORMER FOR EACH 3 MOLES OFTHE LATTER.